Substituted 9, 10-ethanoanthracene compounds and method for their preparation



United States Patent O No Drawing. Filed Dec. 21, 1959, Ser. No. 861,137 14 Claims. (Cl. 260-465) This application is a continuation-in-part of my copending application Serial No. 387,021, filed October 19, 1953, now abandoned, which was a continuation-in-part of my application Serial No, 235,569, filed July 6, 1951, now abandoned.

This invention relates to new compositions of matter and in particularly to nitro-substituted endo anthracene compounds having the general formula 11hi1 R-ONOz \I/ wherein R is an alkyl, halogen, o-carboxyalkyl, w-acyloxya'lkyl, w-carboalkoxyalkyl, cyanoalkyl, w-formylalkyl, or alkylol radical.

The nitro-substituted endo anthracene compounds of this invention are valuable intermediates in the preparation of high explosives. Thus, when these compounds are heated they yield nitroo'lefin compounds having the general formula CH -R he.

wherein R is as defined above. This method of obtaining nitroolefin compounds from the novel endo anthracene compounds of the present invention is more fully disclosed in my copending application Serial No. 861,138, filed concurrently with this application.

The nitroolefins obtained from the compounds of this invention by the pyrolysis method of copending application Serial No. 861,138, in which R is an w-acyloxyalkyl radical such as nitroallyl acetate, readily condense With nitro compounds having a labile hydrogen function, such as methyl 4,4-dinitro'butyrate, to form highly nitrated compounds, such as dimethyl 4,4,6,8,8-pentanitro-1,1l-undecanedioate, useful as high explosives. A more complete description of this process can be found in my copending application Serial No. 636,839, now US. Patent No. 3,000,932, filed January 28, 1957. In addition, all of the nitroolefins obtained by pyrolysis from my novel compositions undergo an addition reaction with polynitr-o compounds having a labile hydrogen function, such as 2,2,4,4-tetranitrobutyl acetate, to form highly nitrated compounds useful as high explosives. 2,2,4,4-tetranitrobu-tyl acetate is disclosed in assignees copending application Serial No. 617,667, filed October 22, 1956, now US. Patent No. 2,880,236. The addition reaction is conducted according to the method set forth in copending application Serial No. 636,839, now US. Patent No. 3,000,932.

The highly nitrated compounds obtained by the abovedescribed methods are useful as high explosives and can be used inany conventional explosive missile, projectile, rocket, or the like, as the main explosive charge. An example of such a missile is disclosed in United States Patent 2,470,162, issued May 17, 1949. One way of using the high explosives of this invention in a device such as that disclosed in United States Patent 2,470,162 is to pack the crystalline explosive in powder form into the warhead of the missile. Alternatively, the crystals can be first pelletized and then packed. A charge thus prepared is sufiioiently insensitive to withstand the shock entailed on the ejection of a shell from a gun barrel or from a rocket launching tube under the pressure developed from ignition of a propellant charge, and can be caused to explode on operation of a nimpactor time-fuse mechanism firing a detonating explosive such as lead azide or mercury fulminate.

Compounds of the present invention are conveniently prepared by condensing 1l-nitro-9,IO-ethanoanthracene with an alkyl halide, a halogen, an alkenoic acid ester, an alkenoic acid, an unsaturated nitrile, an alkanal, or an a,,B'-unsaturated aldehyde in the presence of an alkali metal or alkylene earth metal alcoholate. It is also within the scope of this invention to prepare my novel composiions by'means of a two-step process. For example, 11- nitro-9,IO-ethanoanthracene can first be reacted with an aldehyde such as acetaldehyde to yield an ll-alkylol-llnitro-9,Ill-ethanoanthracene by the method described above and this composition can then be reacted with an anhydride such as acetic anhydride to produce, as a final product, an l l-carboalkoxyalkyl-l1-nitro-9,l0-ethanoanthracene Within the scope of the general formula given above.

Specific examples of suitable reactants are ethyl iodide, butyl chloride, methyl iodide, C1 F ethyl acrylate, methyl methacryla-te, propionaldehyde, acrylic acid, and acrylic aldehyde. These materials react with ll-nitm- 9,10-ethanoanthracene to produce 11-ethyl-11-nitro-9,l0 ethanoanthracene; 11 butyl 11 nitro 9,10 ethanoanthracene; 11 methyl ll-nitro 9,10 ethanoanthracone; ll-chloro-1'1-nitro-9,IO-ethanoanthracene; ll-fiuoro- 11 nitro 9,10 ethanoanthracene 1'1 (2 carboethoxyethyl) 11 nitro 9,10 ethan-oanthracene; 11 (2- carbomethoxy 1 methylethyl) 11 nitro 9,10- ethanoanthracene; ll-(l-hydroxypropyl) 11-nitro-9,l0- ethanoanthracene; l1 (2 carboxyethyl) 11 nitro- 9,10-ethanoanthrene; and 11-(2-formylethyl)-ll-nitro 9,10-ethanoanthracene, respectively.

The alcoholate used may be any of the alkali metal or a-lkaline earth metal alcoholates such as sodium methylate, calcium propionate, lithium ethylate, etc.

The following examples are supplied to more clearly illustrate my invention. It is to be understood, however, that these examples are supplied purely in an illustrative sense and are not intended to impose limitation upon the scope of the invention.

EXAMPLE I Formation of 11-nitro-9,ZO-ethanoanthracene EXAMPLE II Formation of l1-brom01l-nitr0-9,10-2fhianoaltthracene One mole of 1l-nitro-9,IOethanoanthracene is dis solved in methanol and refluxed with one mole of sodium methylate, or other alooholate of an alkali metal dissolved in the particular alcohol used to form the alcoholate, until reaction is complete. After evaporation of the solvent the residue is dissolved in water and a halogen such as bromine is added until there is an ex- HOE Br N02 NaBr EXAMPLE IH Formation of 1 1 -methyll-J1 -nitr0-9,10-

ethanoanthracene One mole of 11-nitro-9,IO-ethanoanthraoene is converted into the acid-sodium .salt by refluxing it until the reaction reaches completion with a solution of sodium methylate in methanol in which about one mole of sodium methylate is employed. The residue obtained after evaporation of the solvent is dissolved in water and one mole of formaldehyde is added. A viscous oil precipitates and the temperature rises somewhat. After two hours a solid material forms which may be filtered off and recrystallized from methanol and isopropyl ether. This compound is 1l-methylol-11-nitro-9, -ethanoanthracene, and has a melting point of l57158 C. The equation involved in this example is as follows:

-|- NaO CH3 H0110 1120 EXAMPLE IV Formation 0 f .11 -acet0xymethyl-1J-nitr0-9,10-

ethanoan thracena The 11 methylol 11 nitro 9,10 ethanoanthracene formed by the preceding procedure may 'be acetylated by treating the compound in a suitable container with acetic anhydride. The ll-acetoxymethyl-ll-nitro- 9,10-ethanoanthracene formed has a melting point of 103105 C. The reaction occurs in accordance with the following general formula:

+ CHaOH NaOH A mixture of one mole of 11-nitro-9,IO-ethanoanthracene is mixed wit-h one mole of sodium methylate in methanol and refluxed for 30 minutes. The solvent is evaporated and the residue dissolved in water. After the addition of one mole of acrylonitrile the mixture is stirred continuously for six hours at about 60 C. A yell-ow oil settles which solidifies when standing over night. The water is decanted. This oil is purified by several crystallizations from isopropyl ether and methanol. The compound thus obtained is 11-(2-cyanoethyl)- 11-nitro-9,IO-ethanoanthracene and has a melting point of 1-1 8-121 C. The reaction is illustrated by the equation H(ill-H N OCH H C CH N H N OH OH OH NC-CH CHr -NO; a 3

EXAMPLE v1 Formation of 1 1 (2 -carbometh0xyethyl 1-nitr0-9,] 0-

ethanoanthracene CHBOH NaOH The above reactions illustrate the manner in which the wide variety of substituted compounds of 11-nitro-9,10- ethanoanthracene can be obtained.

The 11-nitro 9,10-ethanoanthracene starting materials for the method of this invention are prepared by condensing nitroethylene with anthracene in accordance with the reaction scheme set forth below:

HCNO:

This reaction is more fully disclosed in my copending application Serial No. 387,022, filed October 19, 1953, now US. Patent No. 2,945,892.

HCH

The compounds of this invention, as noted above, may be pyrolysed to form the corresponding substituted nitroethylene derivatives which, as explained, are useful in the preparation of high explosives. In addition, the halogen substituted derivatives, such as l-chloro-l-nitroethylene, find valuable use as pharmaceutical intermediates and also as intermediates in the preparation of wetting, detergent, and emulsifying agents as disclosed in US. Patent 2,510,281, issued June 6, 1950, and US. Patent 2,510,282 of the same date.

Reaction temperature is not critical to the novel method of this invention, the only significant effect of temperature variation being a variation in reaction rate.

I claim:

. 1. As compositions of matter, the substituted 9,10- ethanoanthracene compounds having the general formula wherein R is a radical selected from the group consisting of halogen, lower w-carboxyalkyl, and lower w-formyl alkyl radicals.

2. As compositions of matter, the substituted 9,10- ethanoanthracene compounds having the general formula wherein R is a lower w-carboxyalkyl radical.

3. As a composition of matter, ll-acetoxy-methyl-l 1- m'tro-9,IO-ethanoanthracene.

4. As a composition of matter, 11-chloro-11-nitr-o-9,10- ethanoanthracene.

5. The method of preparing compounds having the general formula R(IJNO2 \I/ wherein R is a lower alkyl radical, which comprises reacting l1-nitro-9,IO-ethanoantMacene with a lower alkyl halide in the presence of an alkali metal alcoholate.

6. The method of preparing compounds having the general formula \l/ wherein R is a lower alkylol radical which comprises reacting l1-nitro-9,IO-cthanoanthracene with a lower alkanal in the presence of an alkaline earth metal alcoholate.

7. The method of preparing compounds having the general formula HIGH R-NOz wherein R is a lower w-carboxyalkyl radical which comprises reacting 11 nitr c-9,IO-ethanoanthracene with a lower alkenoic acid in the presence of an alkali metal alcoholate.

8. The method of preparing compounds having the general formula wherein R is a lower cyanoalkyl radical which comprises reacting 1l-nitro-9,10-ethanoanthracene with a lower unsaturated nitrile in the presence of an alkali metal alcoholate.

9. The method of preparing compounds having the general formula 12. The method of preparing l1-(2-cyanoethyl)-ll- Q nitro-9,10-ethanoanthracene which comprises reacting llnitro-9,IO-ethanoanthracene with acrylonitrile in the presence of calcium propionate.

13. The method of preparing II-(Z-carbomethoxyethyl) 11-nitro-9,IO-ethanoanthracene which comprises reacting l1-nitro-9,IO-ethanoanthracene with methyl acrylate in the presence of lithium ethylate.

14. The method of preparing ll-substituted, ll-nitro- 9,10-ethanoanthracene, which comprises reacting ll-nitro- 9,10-ethanoanthracene with a compound selected from the group consisting of halogens, lower alkenoic acids and lower alpha-beta unsaturated aldehydes, in the presence of an alcoholate selected from the group consisting of alkali metal alcoholates and alkaline earth metal a1- coholates.

References Cited by the Examiner Klager: J. Organic Chemistry, volume 20, May 1955, pages 650-656.

REUBEN EPSTEIN, Acting Primary Examiner.

WILLIAM G. WILES, CHARLES B. PARKER, LEON D. ROSDOL, CARL D. QUARFORTH, Examiners. 

1. AS COMPOSITION OF MATTER, THE SUBSTITUTED 9,10ETHANOANTHRACENE COMPOUNDS HAVING THE GENERAL FORMULA 